Isotopic Tracing of Perchlorate Sources in the Environment

Perchlorate (ClO4−) is an emerging persistent pollutant that is ubiquitous in the environment at trace concentrations. Perchlorate ingestion poses a risk to human health because it interferes with thyroidal hormone production. The identification of perchlorate sources in groundwater is a primary concern. Chlorine and multi-oxygen isotopic tracing of perchlorate (δ37Cl, 36Cl/Cl, δ18O, and Δ17O) can provide a unique tool for identifying the origin and transport of perchlorate in groundwater. Along with the kinetic fractionation of chlorine and oxygen isotopes, the Δ17O value, 36Cl/Cl ratio, and ε18O/ε37Cl (the fractionation coefficient of oxygen and chlorine isotopes) are constant, potentially indicating the biodegradation of perchlorate, without disguising its source information. Therefore, comprehensive characterization of stable chlorine and poly-oxygen isotopes is expected to provide direct evidence for identifying the source of perchlorate in groundwater. However, further studies are needed to increase the amount of isotopic data of different perchlorate sources, to make the end-member model available to broader regions. It is critically important to understand the range of values and differences of isotopes among natural perchlorate sources and the perchlorate formation mechanisms.

Chlorine isotopes unravel conditions of formation of the Neoproterozoic rock salts from the Salt Range Formation, Pakistan

During the late Neoproterozoic, the Salt Range in Pakistan was one of the regions where the Tethys truncated and marine strata developed. The numerous transgressions and regressions that occurred during that period provided enough initial material for the development of marine evaporites. The geology of the Salt Range is characterized by the presence of dense salt layers and the existence of four regional and local scale unconformities. These thick salt deposits geologically favor potash formation. Here we coupled chloride isotope geochemistry and classical chemistry of local halite samples to assess the extent of brine evaporation that ultimately formed the salt deposits. Our results indicate that evaporites in the Salt Range area are Br-rich and precipitated from seawater under arid climate conditions. The corresponding δ37Cl values vary from –1.04‰ to 1.07‰, with an average of –0.25‰ ± 0.52‰, consistent with the isotope range values reported for other evaporites worldwide. The positive δ37Cl values we obtained indicate the addition of nonmarine Cl, possibly from reworking of older evaporites, the influx of dilute seawater, the mixing of meteoric and seawater, and the influence of gypsum-dehydration water. The negative Cl isotope compositions (δ37Cl < –1‰) indicate that brines reached the last stages of salt deposition during the late Neoproterozoic. We conclude that the Salt Range Formation could be promising for K-Mg salts.